JPH0660121B2 - Production method of glycerin monoallyl ether - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing glycerin-α-monoallyl ether.

Glycerin monoallyl ether is a compound having two hydroxyl groups and one allyl group, and is therefore used for producing polymers having various characteristics. For example, it is widely used as a raw material for water-soluble resins, urethane rubber vulcanizing agents, anti-scale agents, polyester resin air-drying agents, and the like.

(Prior art and problems to be solved by the invention) In the conventional method of synthesizing 1,2-diol compound by water addition reaction with epoxy compound, efficient reaction is achieved by using a homogeneous catalyst such as sulfuric acid, acetic acid and formic acid. Is known to proceed, and glycerin monoallyl ether can be produced in high yield by a sulfuric acid catalyst even in the reaction of allyl glycidyl ether with water.

However, when sulfuric acid is used as a catalyst, since sulfuric acid is a strong acid and easily corrodes metals, it is necessary to strictly neutralize the sulfuric acid after the reaction, and it is necessary to remove the sulfate salt generated by the neutralization. As a result, there are difficulties such as easy clogging of the machine. Alternatively, it is inconvenient to carry out an operation such as distillation without performing neutralization because the product is decomposed. Furthermore, when a sulfuric acid catalyst is used, the continuous reaction is difficult and the catalyst cannot be recovered.

Attempts have been made to use heterogeneous catalysts to overcome such drawbacks.

For example, it has been reported that an ion exchange resin (“Amberlite IR-120” manufactured by Rohm and Haas Co.) is used when ethylene oxide is reacted with water to produce ethylene glycol (DFOthmer and MSThaker, In.
d. Eng. Chem., 50 , 1235 (1958)).

However, the "Amberlite IR-
When a gel type strong acid cation exchange resin such as 120 "is used in the reaction of allyl glycidyl ether and water,
There are problems that a water-soluble low-boiling product is by-produced, the reaction stops halfway and is not completed, and that the catalyst swells and is crushed to shorten the catalyst life.

(Means for Solving the Problem) The inventors of the present invention have made intensive studies for the purpose of improving the above-mentioned drawbacks and obtaining a heterogeneous catalyst having a long catalyst life and stable even in an organic solvent. As a result, they have found that a specific strong acid cation exchange resin can achieve the above object, and have completed the present invention.

In the present invention, when glycerin monoallyl ether is produced by reacting allyl glycidyl ether with water in the presence of an acid catalyst, the reaction is performed in the presence of an MR type strongly acidic cation exchange resin or polyperfluoroalkyl sulfonic acid resin as an acid catalyst. Is a process for producing glycerin monoallyl ether.

Examples of MR (macroreticular) type strong acid cation exchange resin used in the present invention include "Amberlyst 15" (trade name, manufactured by Organo) and polyperfluoroalkyl sulfonic acid resin such as "Nafion 390". , 321, 415 or 324 "(trade name, manufactured by DuPont) and the like, but from the viewpoint of heat resistance and chemical resistance, a polyperfluoroalkylsulfonic acid resin is preferable. The polyperfluoroalkyl sulfonic acid resin may be one containing a carboxyl residue in the molecule, for example, "Nafion N-901 or N-902" (trade name, manufactured by DuPont).

As the shape of the catalyst, a sheet shape, a granular shape or the like can be used. The amount of the catalyst used is the EW (Equivalent weight) of the resin.
In the case of a batch reaction, for example, when the EW value is 1100, a weight ratio of 0.01 to 1.0 is suitable for allyl glycidyl ether, and in the case of a continuous reaction, 0.001 to 1.0 is suitable. is there.

The resin catalyst, which is a heterogeneous catalyst, can be easily recovered from the reaction solution due to excess and can be reused in the next reaction without reprocessing. The reaction can also be carried out continuously. Since the reaction liquid after removing the catalyst resin is neutral, no post-treatment such as neutralization is required.

Water can be removed by distillation to isolate the product,
If necessary, high-purity glycerin monoallyl ether can be extracted by rectification.

In the present invention, the amount of water used is 2 to 100, preferably 3 to 20, by weight ratio to allyl glycidyl ether. When the weight ratio is less than 2, a high-boiling point product is produced more than the target product glycerin monoallyl ether.
If the weight ratio exceeds 100, the product content in the reaction solution decreases.

Although the reaction proceeds even at room temperature, it is usually carried out by heating in the range of 30 to 100 ° C. to increase the reaction rate and shorten the reaction time.

(Effects of the Invention) The present invention makes it possible to obtain glycerin-α-monoallyl ether of excellent quality because of the presence of an MR type strongly acidic cation exchange resin or a polyperfluoroalkyl sulfonic acid resin as an acid catalyst. Since it is easy to collect, the catalyst can be used successively, and continuous reaction is possible, and there is no problem of corrosion of the reaction apparatus, it can be said to be an industrially excellent production method.

(Example) Example 1 150 ml of water in a 300 ml reactor equipped with a stirrer, a thermometer, and a dropping funnel, perfluoroalkyl sulfonic acid resin ("Nafion 390" manufactured by DuPont, EW = 110).
0) 16 g was added and the mixture was heated with stirring at 45 ° C. 50 ml of allyl glycidyl ether was added with a dropping funnel at a reaction temperature of 50.
Dropwise so as not to exceed ℃, and continue stirring at 50 ℃ for 2 hours.

The catalyst was separated from the reaction solution, water was distilled off under reduced pressure, and the product was purified under reduced pressure to give 98.8% pure glycerin-
α-monoallyl ether was obtained in a yield of 89% (boiling point 1
50 ° C / 10 Torr).

When the catalyst resin recovered above was used to carry out a re-reaction in the same manner as above, the reaction rate did not decrease, and no abnormalities in quality were observed in the product.

Example 2 MR type strong acid cation exchange resin (“Amberlyst 1
5 "Organo Co., EW = 227) 140 ml resin tower (diameter 3 × height 20 cm) was heated to 50 ° C., and 10 kg of allyl glycidyl ether aqueous solution (10 wt%) was added.
Was dripped. After water in the effluent was distilled off under reduced pressure, the product was rectified under reduced pressure to obtain glycerin monoallyl ether in a yield of 91%.

Comparative Example 1 60 ml of water and 0.6 g of sulfuric acid were added to a 100 ml reactor equipped with a stirrer, a thermometer and a dropping funnel and heated to 45 ° C. 34 g of allyl glycidyl ether was added dropwise with a dropping funnel so that the reaction liquid temperature did not exceed 50 ° C., and stirring was continued at 50 ° C. for 1 hour.

After completion of the reaction, analysis by gas chromatography revealed that glycerin monoallyl ether was obtained in a yield of 90%.

The reaction solution was concentrated under reduced pressure without neutralization, and further purification was attempted by distillation under reduced pressure, but glycerin monoallyl ether was not distilled out, and only low-boiling substances of decomposition products were distilled (confirmed by gas chromatography. ).

Comparative Example 2 Instead of the perfluoroalkyl sulfonic acid resin as the catalyst in Example 1, "Amberlite IR-120" was used.
A test was conducted in the same manner as in Example 1 except that (Organo) was used.

After completion of the reaction, by gas chromatography analysis, 12 mol% of low-boiling components was found in addition to 58 mol% of the desired product glycerin monoallyl ether and 30 mol% of the starting material allyl glycidyl ether.

Further, even if the reaction was continued at the same temperature, no reduction of allyl glycidyl ether was observed.

Claims (1)

[Claims] 1. When producing glycerin monoallyl ether by reacting allyl glycidyl ether with water in the presence of an acid catalyst, the reaction is carried out in the presence of MR type strong acid cation exchange resin or polyperfluoroalkyl sulfonic acid resin as an acid catalyst. A method for producing glycerin monoallyl ether, which is characterized in that